Azo-dyes



component .which contains a completely or partly hydrogenatedjcarbonnucleus and which likewise Patented Sept. 22, 1936 UNITE-DYSTATES PATENTOFFICE AZO-DYES Hermann' Rohrbach, Wolfen, Germany, assignor to GeneralAniline Works, Inc., New York, N. Y.,

.a corporation of Delaware 6' Drawing. Application November 14, 1932,

My present invention relates to a procession manufacturing new azo dyesand more particularly of dyes which show an extraordinarily; highsolubility in organic solvents, oils, fats, waxes is'fre'e' ofgroups'efiecting a solubility in water. The dyes thus obtained areextraordinarily soluble in organ'ic solvents, oils, fats,lwaxes andproducts produced therefrom andthusihavea wide field'of application.'Thedyeings obtained, show a good or evenvery good fastness to light andfastnessto sublimation. When compared with the known azo dyes'containingno or only one hydrogenated nucleus, the new dyes containing at least{two hydrogenated nuclei in their molecule are distinguished by theirextremely enhanced solubility in the solventsgenerally dyed with theso-called fat dyes (Sudan .dyes) The invention is illustrated by thefollowing examples, the parts being by weight:'-

Example 1. 29.4 parts of 1-c'li-(3-methyl-4- aminophenyl)-hexahydrobenzene of l the iormula CH2 are dissolved while gentlywarmin'giri 500parts of water and 60 parts oi hydrochloric acid of 20 B.and bisdiazotized at a temperature of to Q. with 13.8 parts of sodiumnitrite dissolved in water.v The clear solution otthe bisdiazocompoundis allowed to run slowly into a suspension of 36 .'parts' of1-(4hydroxyphenyl) -hexahydrobenzene in 2000 parts of water and 14partsof I sodium hydroxide cooled to 0 C. The coupling Serial No.1642,681. In Germany November 16 Claims. I (01. 124-1) finished, theseparated dye is filtered ofi, pressed, dried at about 50 C. and thenground. It is easily soluble toa deep yellow solution in the usual organic solvents and likewise in fats, oils and waxes. The coloringsprepared with this dye are extraordinarily fast to light and tosublimation.

In the foregoing example, 1-di-(3-methyl-4- aminophenyl)-hexahydrobenzene may be substituted with the same effect by1-di-(3-methyl-4- aminophenyl) hexahydro-4-methylbenzene obtainable from4 m'ethylcyclohexanoneand 2- phenyl)' hexahydrobenzene are bisdiazotizedas indicated in Example 1 and coupled with a $0111 tion of '31 parts of1.2.3.4-tetrahydro-7-hydroxynaphthalene in 500 parts of water and llparts of sodium hydroxide at a temperature of 0 to 3 C. ,Thedye isworked up as indicated in Example 1. It dissolves well to an orangesolution in-the media enumerated in Example 1 and likewise isextraordinarily:fast to light and sublimation.

Example 3 -13;!) parts 'of 1-(3-methyl-4- aminophenyl)-hexahydrobenzenewhich may be represented by j i l 011F011:

are dissolved in 500Vparts of hot water and 15 parts of hydrochloricacid of 20 B. and precipitated inthe form of the hydrochloride by afurther addition of 15 parts of hydrochloric acid of 20 B. By additionof 6.9 parts of sodium nitrite dissolved in water, diazotization iscarried out at to C., whereupon the clear solution of the diazo compoundis allowed torun into a suspension of 18 partsof,1-(4-hydroxyphenyl)-hexahydrobenzene in 1000 partsof water and 7parts of sodium hydroxide cooled to 0 C. The dye dissolves in organicsolvents to a greenish yellow solution and has the properties named inExamples 1 and 2.

Ewample 4.22.35 parts of 1-(3(?)-methyl 4 2) -amino-6 -chlorophenyl)-hexahydroben zene (obtainable according to the process disclosedbyBodroux, in C. R. 1928, vol. 186, page 1005, by condensation ofcyclohexene with 4-chloro-1- methylbenzene, nitration of thecondensation product and reduction) are emulsified by rapidly 39likewise isjfast to sublimation.

stirring in 50O parts of hot water. This emulsion is converted in asuspension of the hydrochloride suspended in water, are added,whereafter the free hydrochloric acid formed is substituted by acetic,acid by Slowly adding a dilute solution of sodium acetate. the'dyeis.formed, the latter is'pressed and carefully dried. It is easily solubleto a greenish yellow' solution in the media previously named and,

The following table shows a. number of other dyesobtainable according tothe new processand indicates the shadesobtainable therewith.

q igg ggg Coupling component Shade 1 di (4 aminophenyl)l-(4-hydroxyphenyl)- Greenishhexahydrobenzene hexahydrobenzene yellow 1di (3 metboxy 4 amino 1 (4-hydroxyphenyD- Orange phenyl)'--hexahydrobenhexahydrobenzene zene 1 (3 methyl 4'- amino 1.2.3.4-tetrahydro-8- Brownphenyl) hexahydroben hydroxynaphthazene lone 1 (3.6 dimethy1(?) amino 1-(4-hydroxyphenyl)- Yellow phenyl) hexahydrobon hexahydrobenzene zone 1(3(?) methyl 4(7) 1.2.3.:i-tetrahydro-7- Orange amino- 6(?)chlorophenyl).- ammonaphthalene. Y hexahydtobenzene 1 (4 aminophenyl)hexa 1- (4-hydroxyphenyl)- Greenlshhydrobenzene, hexahydrobenzene.yellow 1 di (3, methyl-4 ammo v1 (4-hydroxyphenyl)-- Yellow phenyl)hexahydroben 2.3.4.5 tetrahydro zene .benzene.

The 1-(3.6-dimethyl aminophenyD-hexahydrobenzene (of. the first columninJshe foregoing tablelis obtainable in as'imilar, manner as thestarting material mentioned Example 4 accord- ,ing to Bodrouxs process,by condensation of 'cyclohexehe with Xylene, nitration of the condensa--tion product and reduction. In ,an analogous manner other substitutionproducts of 1-(aminophenyl) -hexahydrobenzene are obtainable by 6choosing the correspondent starting materials;

It is obvious that my invention is not limited to the foregoing examplesor to the specific details" given therein. Thus, for instance, I may useas starting materials a monoor di(aminophenyl)- hexahydrobemzene whichcontains other substi-- When no further amount of whereinx'and a." meanhydrogen, alkyl, halogen,

. alkoxy, R means a hydrophenylhydroxybenzene-,

a. hydrophenylaminobenzene-, a tetrahydrohydroXynaphthaleneatetrahydroaminonaphthalene-, or an Na-eyclohexylaniline radicle and Z ishydrogen or identical with the bracketed part of the formula.

2. The new azo dyes. being easily soluble in. organic solvents, oils,fats, waxes and products made therefrom, and corresponding to. thegeneral formula wherein a: and mean hydrogen, alkyl, halogen, alkoxy andZ' is hydrogen or identical with the bracketed part of the formula.

3. The yellow to greenish yellow azo dyes being easily soluble inorganic solvents, oils, fats, waxes, andproducts made therefrom, andcorresponding to the formula wherein a: and a." mean hydrogen, halogen,alkyl or alkoxy. I

4. The yellow to greenish yellow azo dyes being easily soluble inorganic solvents, oils, fats, waxes, and products madetherefrom, andcorresponding to the formula wherein :a ands," mean hydrogen, halogen,alkyl oralkoxy. @1;

' 5. The greenish yellow azo dye being easily soluble in organicsolvents, oils, fats, waxes, and products made therefrom, andcorresponding to the formula om 0H 7 I w E20 CH2? on me orn .6.,Theyellow azo dye being easily soluble in organic solvents, oils, fats,waxes, and products made therefrom, and corresponding to the formula CH2CH2 '7. The process which comprises diazotizing a compound of thegeneral formula wherein a: and 3: mean hydrogen, alkyl, halogen oralkoxy and Z is hydrogen or identical with the bracketed part of theformula, and coupling the diazo compound with an azocomponentpcontaining a hydrogenated carbon nucleus.

8. The process which comprises diazotizing a compound of the generalformula Z I a;

H2C3 (13H:

wherein a: and 3: mean hydrogen, alkyl, halogen or alkoxy and Z ishydrogen or identical with the bracketed part of the formula andcoupling the diazo compound with 1-(4-hydr0xyphenyl)- hexahydrobenzene.

9. The process which comprises diazotizing al-(phenylamino)-hexahydrobenzene of the formula 1 i l wherein a: and 1:mean hydrogen, alkyl, halogen or alkoxy and coupling it with1-(4-hydroxyphenyl) -hexahydrobenzene.

10. The process which comprises diazotizing al-di-(phenylamino)-hexahydrobenzene of the formula 20 wherein a: and.17' mean hydrogen, alkyl, halogen or alkoxy and coupling it with l-(l-hydroxyphenyl) -hexahydrobenzene.

11. A composition substantially comprising an azo dye corresponding tothe general formula 35 wherein a: and :0 mean hydrogen, alkyl, halogen,alkoxy, and Z is hydrogen or identical with the 75 bracketed part oftheformula, and a hydrocarbon or oXy-hydrocarbon material, which is capableof being dyed by said azo dye, of the group consisting of hydrocarbons,halogenated hydrocarbons, alcohols, ethers, esters, acetone,

. fats, oils, waxes, resins, and higher fatty acids.

13. A composition substantially comprising an azo dye corresponding tothe general formula.

wherein a: and ac means hydrogen, halogen,

alkyl or alkoxy, and a hydrocarbon or oxy-hydrocarbon material, which iscapable of being dyed I by said azo dye, of the group consisting ofhydrocarbons, halogenated hydrocarbons, alcohols, ethers, esters,acetone, fats,,oils, waxes, resins, and higher fatty acids.

14. A composition substantially comprising an azo dye corresponding tothe formula wherein :n and at mean hydrogen, halogen, alkyl or alkoxy,and a hydrocarbon or oxy-hydrocarbon material, which is capable of beingdyed by said azo dye, of the group consisting of hydrocarbons,halogenated hydrocarbons, alcohols, ethers, esters, acetone, fats, oils,waxes, resins,

I and higher fatty acids.

(13H: CH2

15. A composition substantially comprising an azo dye corresponding tothe general formula OH; OH

and a hydrocarbon or oxy-hydrocarbon material, which is capable of beingdyed by said azo dye, of the group consisting of hydrocarbons,halogenated hydrocarbons, alcohols, ethers, esters, acetone, fats, oils,waxes, resins, and higher fatty acids.

HERMANN ROHRBACH.

